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    • 专利摘要:
    A resist material containing a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the formula (1). In formula, R <1> represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R <2> represents a hydrogen atom, a hydroxyl group, a halogen atom, or a trifluoromethyl group, n Is 0 or a positive integer of 1 to 4; According to the present invention, the alkali dissolution rate contrast before and after exposure is greatly increased by blending tert-amyloxystyrene with a reactive resin which decomposes under the action of an acid to increase its solubility in alkali, as a base resin. Highly sensitive and highly sensitive, when tert-butoxy styrene is used, high resolution in a baking temperature range of 100 to 110 ° C, which is difficult, can be realized.
    公开号:KR20030052966A
    申请号:KR1020020066035
    申请日:2002-10-29
    公开日:2003-06-27
    发明作者:다까노부 다께다；오사무 와따나베；가즈노리 마에다；히로시 미야꼬시
    申请人:신에쓰 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Resist Material and Pattern Forming Method {Resist Composition and Patterning Process}
    [1] The present invention has a wide baking temperature range by blending a high molecular compound containing tert-amyloxystyrene as a base resin into a resist material as a reactive group that decomposes under the action of an acid and increases its solubility in alkali. The present invention relates to a resist material such as a chemically amplified positive resist material and a pattern forming method, which are particularly preferable as a fine pattern forming material for ultra-LSI manufacturing, having a high alkali dissolution rate contrast, high sensitivity, high resolution, and excellent etching resistance. .
    [2] In recent years, with the higher integration and higher speed of LSI, finer pattern rules have been required, and far-infrared lithography is promising as a next generation fine processing technology. Ultraviolet lithography can also process 0.5 micrometers or less, and when the resist material with low light absorption is used, pattern formation with a sidewall close to perpendicular | vertical to a board | substrate becomes possible.
    [3] Recently developed acid-catalyzed chemically amplified positive resist materials (described in Japanese Patent Application Laid-Open No. 2-27660, Japanese Patent Application Laid-Open No. 63-27829, etc.) are KrF excimer lasers of high brightness as ultraviolet light sources. Using is expected to be a particularly promising resist material for far-ultraviolet lithography having high sensitivity, resolution, and dry etching resistance and excellent characteristics.
    [4] As such a chemically amplified positive resist material, a three-component system composed of a base polymer, a two-component system composed of an acid generator, a base polymer, an acid generator, and a dissolution inhibiting agent having an acid labile group is known.
    [5] For example, Japanese Patent Laid-Open No. 62-115440 proposes a resist material composed of poly-p-tert-butoxystyrene and an acid generator, and similar to this proposal, Japanese Patent Laid-Open No. 3-223858. In the two-component resist material consisting of a resin having a tert-butoxy group in the molecule and an acid generator, Japanese Patent Application Laid-Open No. 4-211258 discloses a methyl group, isopropyl group, tert-butyl group, tetrahydropyranyl group, trimethyl A two-component resist material composed of silyl group-containing polyhydroxystyrene and an acid generator has been proposed.
    [6] In addition, Japanese Patent Laid-Open No. 6-100488 discloses poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene] And resist materials comprising polydihydroxystyrene derivatives such as poly [3,5-bis (2-tetrahydropyranyloxy) styrene] and an acid generator have been proposed.
    [7] However, the base resins of these resist materials have a high baking optimum temperature of around 130 ° C. when the acid labile group is tert-butyl group and a low resolution when tert-butoxycarbonyl group has a pattern shape of the resist material. Since alkoxyalkyl groups, such as ethoxyethyl groups, decompose in weak acid, on the other hand, have a drawback that the pattern shape is remarkably thin with time from exposure to heat treatment, the resist film due to miniaturization It is a phenomenon that it is hard to cope with thinning of the thickness and has a bulky group in the side chain, and thus all have problems such as poor heat resistance, inability to satisfy sensitivity and resolution, and have not yet been put to practical use.
    [8] In addition, a resist material using a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary ester has also been reported in order to realize higher transparency and adhesion to the substrate, to improve the drag phenomenon to the substrate, and to improve the etching resistance. (Japanese Patent Laid-Open No. 3-275149 and Japanese Patent Laid-Open No. 6-289608), this type of resist material had problems such as heat resistance and poor pattern shape after exposure, which was not satisfactory. .
    [9] In addition, as the resolution increases, the pattern is thinned at the same time, and accordingly, a resist material having higher etching resistance is desired.
    [10] SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a high sensitivity, a high resolution, an exposure margin, and a process adaptability exceeding a conventional positive resist material, a pattern shape after exposure is good, and a bake temperature width is wide; In particular, it is an object to provide a chemically amplified positive resist material.
    [11] MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the high molecular compound which has a repeating unit represented by following formula (1) or (2), and whose weight average molecular weight is 1,000-500,000 is a positive resist material, especially a chemical amplification positive type Effective as a base resin for resist materials, the chemically amplified positive resist material containing the polymer compound, an acid generator, and an organic solvent increases the dissolution contrast of the resist film, and has high resolution, exposure margin, and wide baking temperature. Therefore, it was found that it was excellent in process adaptability, and the pattern shape after exposure was good, and it could cope with thinning of the resist film thickness according to miniaturization, and found out that it was highly practical in this regard and was quite effective as a resist material for ultra-LSI. .
    [12] Accordingly, the present invention provides the following resist material and pattern forming method.
    [13] Article 1:
    [14] A resist material comprising a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following formula (1).
    [15] <Formula 1>
    [16]
    [17] In formula, R <1> represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R <2> represents a hydrogen atom, a hydroxyl group, a halogen atom, or a trifluoromethyl group, n Is 0 or a positive integer of 1 to 4;
    [18] Article 2:
    [19] A resist material comprising a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following formula (2).
    [20]
    [21] In formula, R <1> , R <3> represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R <2> represents a hydrogen atom, a hydroxy group, a halogen atom, or a trifluoromethyl group R 4 represents a hydrogen atom, a halogen atom, a trifluoromethyl hydroxymethyl group, or -OR, and R represents a linear, branched or cyclic alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or Represents a trialkylsilyl group, R 5 represents a hydrogen atom or a methyl group, R 6 represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, a halogen atom or a trifluoromethyl group, and R 7 represents a straight chain having 4 to 30 carbon atoms. Chain, branched or cyclic alkyl group, n is 0 or a positive integer of 1 to 4, m is 0 or a positive integer of 1 to 5, p, r, s is 0 or positive , Q is a positive number.
    [22] Article 3:
    [23] (A) an organic solvent,
    [24] (B) the polymer compound according to claim 1 or 2 as a base resin,
    [25] (C) acid generator
    [26] A chemically amplified positive resist material comprising a.
    [27] Article 4:
    [28] (A) an organic solvent,
    [29] (B) the polymer compound according to claim 1 or 2 as a base resin,
    [30] (C) an acid generator,
    [31] (D) Dissolution stopper
    [32] A chemically amplified positive resist material comprising a.
    [33] Article 5:
    [34] (E) The chemically amplified positive resist material according to claim 3 or 4, further comprising a basic compound as an additive.
    [35] Article 6:
    [36] The process of apply | coating the resist material of any one of Claims 3-5 on a board | substrate, and then heat-processing, exposing with high energy rays or an electron beam through a photomask, and heat-processing as needed. And developing using a developing solution.
    [37] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
    [38] The resist material of the present invention is particularly preferably used as a positive type, especially a chemically amplified positive type resist material, and has a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following general formula (1), preferably the following general formula (2): A high molecular compound is contained as a base resin.
    [39] <Formula 1>
    [40]
    [41] In the formula, R 1 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R 2 represents a hydrogen atom, a hydroxy group, a halogen atom, or a trifluoromethyl group, n Is 0 or a positive integer of 1 to 4;
    [42] <Formula 2>
    [43]
    [44] In formula, R <1> , R <3> represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R <2> represents a hydrogen atom, a hydroxy group, a halogen atom, or a trifluoromethyl group R 4 represents a hydrogen atom, a halogen atom, a trifluoromethyl hydroxymethyl group, or -OR, and R represents a linear, branched or cyclic alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or Represents a trialkylsilyl group (in addition, an oxygen atom, etc. may be mentioned as a hetero atom), R <5> represents a hydrogen atom or a methyl group, R <6> represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, a halogen atom, or tri represents a methyl group fluoro, R 7 is a positive integer of 4 to 30 carbon atoms of straight, branched or cyclic alkyl group, n is 0 or 1 to 4, m is 0, It is a positive integer of 1 to 5. p, r, s is zero or positive and q is positive.
    [45] Here, as a linear or branched alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, iso-butyl group, tert- butyl group etc. can be illustrated.
    [46] In the above R 4 , when OR represents the function of an acid labile group, R is selected in various ways, but in particular, a group represented by the formulas (3) and (4), a linear, branched or cyclic tertiary alkyl group having 4 to 20 carbon atoms , An oxoalkyl group having 4 to 20 carbon atoms, a tetrahydropyranyl group, a tetrahydrofuranyl group or each alkyl group is preferably a trialkylsilyl group having 1 to 6 carbon atoms.
    [47]
    [48]
    [49] In formula, R <8> , R <9> , R <11> , R <12> may respectively independently represent a hydrogen atom or a C1-C8 linear or branched alkyl group, and R <10> may interrupt the C1-C18 oxygen atom. Monovalent hydrocarbon groups such as an alkyl group, and R 8 and R 9 , R 8 and R 10 , R 9 and R 10 may be bonded to each other to form a ring, and in the case of forming a ring, R 8 , R 9 , R 10 each represents a linear or branched alkylene group having 1 to 18 carbon atoms, R 13 represents a linear, branched or cyclic alkyl group having 4 to 40 carbon atoms, and a is an integer of 0 or 1 to 4; .
    [50] Here, as the acid labile group represented by the formula (3), specifically, a methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, iso-propoxyethyl group, n-butoxyethyl group, iso-butoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group, etc. are mentioned. On the other hand, examples of the acid labile group of formula (4) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, ethylcyclopentyloxycarbonyl group, ethylcyclohexyloxycarbonyl group, and methylcyclopentyloxycarbonyl group.
    [51] In said R <1> , R <2> , R <3> , R <4> and R <6> , when they represent a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are preferable.
    [52] When the alkyl group of R <7> is a tertiary alkyl group, various selection is carried out, but group represented by following formula (5) and 6 is especially preferable.
    [53]
    [54] In formula, R <14> is methyl group, ethyl group, isopropyl group, cyclohexyl group, cyclopentyl group, vinyl group, acetyl group, phenyl group, benzyl group or cyano group, b is an integer of 0-3.
    [55] Specific examples of the cyclic alkyl group represented by the formula (5) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-isopropylcyclopentyl, 1-vinylcyclopentyl, 1-acetylcyclopentyl, 1-phenylcyclopentyl and 1-sia Nocyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-vinylcyclohexyl, 1-acetylcyclohexyl, 1-phenylcyclohexyl, 1-cyanocyclohexyl, and the like. Although five-membered ring is especially preferable.
    [56]
    [57] In the formula, R 15 is a methyl group, ethyl group, isopropyl group, cyclohexyl group, cyclopentyl group, vinyl group, phenyl group, benzyl group or cyano group.
    [58] Specific examples of the formula (6) include t-butyl group, 1-vinyldimethylmethyl, 1-benzyldimethylmethyl, 1-phenyldimethylmethyl, 1-cyanodimethylmethyl and the like. Moreover, the alkyl group used as the tertiary ester illustrated by General formula (5a-5d) is also preferable as R <7> .
    [59]
    [60]
    [61]
    [62]
    [63] In consideration of the properties of the resist material, in the above formula (2), q is a positive number, p, r, and s are each 0 or a positive number, and the number satisfies the following formula.
    [64] 0 <q / (p + q + r + s) ≦ 0.5, more preferably 0 <q / (p + q + r + s) ≦ 0.3. 0 ≦ p / (p + q + r + s) ≦ 0.8, more preferably 0.3 ≦ p / (p + q + r + s) ≦ 0.8. 0 ≦ r / (p + q + r + s) ≦ 0.35. 0 ≦ s / (p + q + r + s) ≦ 0.35. In this case, p + q + r + s = 1.
    [65] When q becomes 0 and the high molecular compound of Formula 2 becomes a structure which does not contain this unit, contrast of an alkali dissolution rate will disappear, and resolution will worsen. Moreover, when the ratio of p is larger than 0.8, the alkali dissolution rate of an unexposed part will become large too much. In addition, p, q, r, and s can arbitrarily perform the dimension control of a pattern and the shape control of a pattern by selecting the value suitably within the said range.
    [66] The weight average molecular weight of the high molecular compound of this invention needs to be 1,000-500,000, Preferably it is 2,000-30,000. If the weight average molecular weight is less than 1,000, the resist material is inferior in heat resistance. If the weight average molecular weight is larger than 500,000, alkali solubility is lowered, and the phenomenon of dragging after pattern formation tends to occur.
    [67] In addition, in the polymer compound of the present invention, when the molecular weight distribution (Mw / Mn) of the multicomponent copolymer of the general formula (2) is wide, the ratio of low molecular weight or high molecular weight polymer is increased, so that the foreign material on the post-exposure pattern This may be seen or the shape of the pattern deteriorates. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a resist material which is preferably used for fine pattern dimensions, the molecular weight distribution of the multicomponent copolymer to be used is 1.0 to 2.0, It is especially preferable that it is narrowly dispersed to 1.0-1.5.
    [68] One method for synthesizing these high molecular compounds is to heat-polymerize the acetoxystyrene monomer, (meth) acrylic acid tertiary ester monomer and amyloxystyrene monomer by adding a radical initiator in an organic solvent, and the obtained high molecular compound is alkali in an organic solvent. By hydrolyzing and deprotecting an acetoxy group, the high molecular compound of the three-component copolymer of hydroxy styrene, (meth) acrylic acid tertiary ester, and amyloxy styrene can be obtained. Toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, etc. can be illustrated as an organic solvent used at the time of superposition | polymerization. Examples of the polymerization initiator include 2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate) and benzoyl Peroxide, lauroyl peroxide, etc. can be illustrated, A polymerization temperature becomes like this. Preferably it is 50-80 degreeC. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. Ammonia water, triethylamine, etc. can be used as a base at the time of alkali hydrolysis. The reaction temperature is -20 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.
    [69] In addition, it is also possible to introduce | transduce the acid labile group represented by General formula (3) and general formula (4) with respect to a phenolic hydroxyl group part after isolation of the high molecular compound obtained in this way. For example, it is also possible to obtain a high molecular compound in which a phenolic hydroxyl group is partially protected by an alkoxyalkyl group by reacting the phenolic hydroxyl group of the high molecular compound with the high molecular compound in the presence of a base using a halogenated alkyl ether compound.
    [70] At this time, as a reaction solvent, aprotic polar solvents such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide are preferable, and may be used alone or in combination of two or more thereof. As a base, triethylamine, pyridine, diisopropylamine, potassium carbonate, etc. are preferable, and the usage amount is 10 mol% or more with respect to 1 mol of all-phenolic hydroxyl groups of the reacting high molecular compound. The reaction temperature is -50 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.
    [71] In addition, introduction of the acid labile group represented by the above formula (4) can also be carried out by reacting a dialkyl dicarbonate compound or an alkoxycarbonylalkyl halide with a high molecular compound in the presence of a base in a solvent. As the reaction solvent, aprotic polar solvents such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide are preferable, and may be used alone or in combination of two or more thereof.
    [72] The base is preferably triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate, and the like, and the amount thereof is preferably 10 mol% or more with respect to 1 mol of the all-phenolic hydroxyl group of the original high molecular compound.
    [73] The reaction temperature is 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time is 0.2 to 100 hours, preferably 1 to 10 hours.
    [74] Examples of the dialkyl dialkyl compound include di-tert-butyl dicarbonate, di-tert-amyl bicarbonate, and the like. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride and tert-amyloxycarbonylmethyl. Chloride, tert-butoxycarbonylmethylbromide, tert-butoxycarbonylethylchloride and the like.
    [75] However, it is not limited to these synthetic methods.
    [76] In the chemically amplified positive resist material of the present invention, examples of the organic solvent of component (A) include butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and cyclo Pentanone, 3-ethoxyethylpropionate, 3-ethoxymethylpropionate, 3-methoxymethylpropionate, methyl acetacetate, ethyl acetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ butyrolactone, fr Although propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, lactic acid propyl, tetramethylene sulfone etc. are mentioned, but it is not limited to these. Especially preferred are propylene glycol alkyl ether acetates and lactic acid alkyl esters. These solvents may be individual or may mix 2 or more types. Examples of preferred mixed solvents are propylene glycol alkyl ether acetates and lactic acid alkyl esters.
    [77] In addition, the alkyl group of the propylene glycol alkyl ether acetate in this invention has a C1-C4 thing, for example, a methyl group, an ethyl group, a propyl group, etc. are mentioned, Especially, a methyl group and an ethyl group are preferable. Moreover, this propylene glycol alkyl ether acetate has 1, 2 substituents, and 1, 3 substituents, and there exist three types of isomers by combination of substitution positions, and may be individual or a mixture of them.
    [78] Moreover, the alkyl group of the said lactic acid alkyl ester has a C1-C4 thing, for example, a methyl group, an ethyl group, a propyl group, etc. are mentioned, Especially, a methyl group and an ethyl group are preferable.
    [79] The resist material of the present invention may be prepared in a known composition except for using the polymer compound as a base resin, and a known ingredient may be used as a compounding component. In particular, in the case of using a chemically amplified positive resist material, It is desirable to.
    [80] (A) an organic solvent,
    [81] (B) the polymer compound as a base resin,
    [82] (C) an acid generator.
    [83] In this case, as required
    [84] (D) Dissolution stopper
    [85] Is formulated, and preferably
    [86] (E) basic compounds
    [87] Is blended.
    [88] When adding propylene glycol alkyl ether acetate as a solvent, it is preferable to set it as 50 weight% or more with respect to the whole solvent, and when adding lactic acid alkylester, it is preferable to set it as 50 weight% or more with respect to the whole solvent. Moreover, when using the mixed solvent of propylene glycol alkyl ether acetate and lactic acid alkyl ester as a solvent, it is preferable that the total amount is 50 weight% or more with respect to all the solvents. In this case, More preferably, it is preferable to make propylene glycol alkyl ether acetate 60-95 weight% and the lactic acid alkylester the ratio of 5-40 weight%. When there is little propylene glycol alkyl ether acetate, there exist problems, such as applicability deterioration, and when too much, there exists a problem of insufficient solubility, particle | grains, and foreign material generation. When there are few lactic acid alkyl esters, there exist problems, such as insufficient solubility, an increase in particle | grains, a foreign material, etc., When there are too much lactic acid, a viscosity will become high, applicability | paintability worsens, and there exists a problem of deterioration of storage stability. The amount of these solvents added is 300 to 2,000 parts by weight, preferably 400 to 1,000 parts by weight, based on 100 parts by weight of the solid content of the chemically amplified positive resist material, but is not limited thereto.
    [89] As a photo-acid generator of (C) component, as long as it is a compound which generate | occur | produces an acid by high energy ray irradiation, it may be any. Preferred photoacid generators include sulfonium salts, iodonium salts, sulfonyl diazomethane, N-sulfonyloxyimide acid generators and the like. Although it mentions in detail below, these can be used individually or in mixture of 2 or more types.
    [90] Sulfonium salts are salts of sulfonium cations and sulfonates, and as sulfonium cations, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) phenylsulfonium, Tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl ) Sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl ) Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) Sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4 Hydroxyphenyl dimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium And 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, and the like. Examples of the sulfonate include trifluoromethanesulfonate, nonafluorobutanesulfonate and heptadecafluoro. Octanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and the like, and combinations thereof A tan salt is mentioned.
    [91] Iodonium salts are salts of iodonium cations and sulfonates, such as diphenyl iodonium, bis (4-tert-butylphenyl) iodonium, 4-tert-butoxyphenylphenyl iodonium, and 4-methoxyphenylphenyl iodonium. Trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate as aryliodonium cations and sulfonates of , 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octane Sulfonates, dodecylbenzenesulfonates, butanesulfonates, methanesulfonates, and the like, and iodonium salts of these combinations may be mentioned.
    [92] Examples of sulfonyl diazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane and bis (1,1-dimethylethyl Sulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) Diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenyl Sulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, tert-butoxycarbonyl-4-methylphenylsulfonyl Bissulfonyl diazomethane, such as diazomethane, and sulfonyl carbonyl diazomethane are mentioned.
    [93] Examples of the N-sulfonyloxyimide type photoacid generator include succinic acid imide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyl dicarboxylic acid imide, and 5-norbornene-2,3-dicarboxylic acid Imide skeletons such as imide, 7-oxabicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid imide, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadeca Fluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfo And compounds of a combination of a nate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.
    [94] Examples of the benzoin sulfonate type photoacid generator include benzointosylate, benzoin mesylate, benzoin butanesulfonate, and the like.
    [95] As a pyrogallol trisulfonate-type photo-acid generator, all the hydroxyl groups of a pyrogallol, a fluoroglycine, a catechol, a resorcinol, and a hydroquinone are all a trifluoromethane sulfonate, a nonafluoro butane sulfonate, and a heptadeca Fluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfo And compounds substituted with nate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate and the like.
    [96] As a nitrobenzyl sulfonate type photo-acid generator, 2, 4- dinitro benzyl sulfonate, 2-nitro benzyl sulfonate, 2, 6- dinitro benzyl sulfonate is mentioned, As a sulfonate, a trifluoro specifically, is mentioned. Methanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4 -Fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, and the like. Moreover, the compound which substituted the nitro group of the benzyl side by the trifluoromethyl group can also be used similarly.
    [97] Examples of sulfone type photoacid generators include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, 2,2 -Bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) 2- (p-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one, etc. are mentioned.
    [98] Examples of the glyoxime derivative type photoacid generator include bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o -(p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedioneglyoxime, bis-o- (p-toluenesulfonyl)- 2-methyl-3,4-pentanedioneglyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, Bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedioneglyoxime, bis-o- (n-butanesul Ponyl) -2-methyl-3,4-pentanedioneglyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime , Bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (purple Luorooctanesulfonyl) -α-dimethylglycol Shim, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α -Dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl ) -α-dimethylglyoxime etc. are mentioned.
    [99] Among them, preferred photoacid generators include sulfonium salts, bissulfonyl diazomethane and N-sulfonyloxyimide.
    [100] Although the anion of an optimally generated acid differs by the breakability of the acid labile group used for a polymer, etc., the thing which generally does not have volatility and is not extremely high diffusivity is selected. Preferred anions in this case are benzenesulfonate anion, toluenesulfonate anion, 4- (4-toluenesulfonyloxy) benzenesulfonate anion, pentafluorobenzenesulfonate anion, 2,2,2-trifluoroethanesulfonic acid anion, nonafluoro Butanesulfonic acid anion, heptadecafluorooctane sulfonic acid anion, and campasulfonic acid anion.
    [101] The addition amount of the photoacid generator (C) in the chemically amplified positive resist material of the present invention is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight based on 100 parts by weight of the base resin as the component (A) in the resist material. to be. The said photo-acid generator (C) can be used individually or in mixture of 2 or more types. Moreover, the transmittance | permeability in a resist film can also be controlled by the addition amount using the photo-acid generator with low transmittance | permeability in an exposure wavelength.
    [102] As a dissolution inhibiting agent of (D) component, the weight average molecular weight is 100-1,000, and the hydrogen atom of the phenolic hydroxyl group of the compound which has 2 or more phenolic hydroxyl groups in a molecule | numerator is 10-100 mol on average as a whole by acid labile group. The compound substituted by the ratio of% is preferable. In addition, the weight average molecular weight of the compound is 100 to 1,000, preferably 150 to 800. The compounding quantity of a dissolution inhibitor is 0-50 weight part with respect to 100 weight part of base resins, Preferably it is 5-50 weight part, More preferably, it is 10-30 weight part, It can use individually or in mixture of 2 or more types. . When there is little compounding quantity, there may be no resolution improvement, and when too large, the film | membrane shrinkage of a pattern will arise and there exists a tendency for the resolution to fall.
    [103] Examples of the dissolution inhibiting agent of the component (D) used preferably include bis (4- (2'-tetrahydropyranyloxy) phenyl) methane and bis (4- (2'-tetrahydrofuranyloxy) phenyl) methane , Bis (4-tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1 '-Ethoxyethoxy) phenyl) methane, bis (4- (1'-ethoxypropyloxy) phenyl) methane, 2,2-bis (4'-(2 ''-tetrahydropyranyloxy)) propane , 2,2-bis (4 '-(2' '-tetrahydrofuranyloxy) phenyl) propane, 2,2-bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4' -tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 '-(1' '-ethoxyethoxy ) Phenyl) propane, 2,2-bis (4 '-(1' '-ethoxypropyloxy) phenyl) propane, 4,4-bis (4'-(2 ''-tetrahydropyranyloxy) phenyl) Tertbutyl valeric acid, 4,4-bis (4 '-(2') '-Tetrahydrofuranyloxy) phenyl) valeric acid tertbutyl, 4,4-bis (4'-tert-butoxyphenyl) valeric acid tertbutyl, 4,4-bis (4-tert-butoxycarbonyloxy Phenyl) valeric acid tertbutyl, 4,4-bis (4'-tert-butoxycarbonylmethyloxyphenyl) valeric acid tertbutyl, 4,4-bis (4 '-(1' '-ethoxyethoxy) Phenyl) valeric acid tertbutyl, 4,4-bis (4 '-(1' '-ethoxypropyloxy) phenyl) valeric acid tertbutyl, tris (4- (2'-tetrahydropyranyloxy) phenyl) methane , Tris (4- (2'-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4- tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1'-ethoxyethoxy) phenyl) methane, tris (4- (1'-ethoxypropyloxy) phenyl) methane, 1,1,2 -Tris (4 '-(2' '-tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4'-(2 ''-tetrahydrofuranyloxy) phenyl) ethane, 1,1 , 2-tris (4 ' -tert-butoxyphenyl) ethane, 1,1,2-tris (4'-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4'-tert-butoxycarbonylmethyloxy Phenyl) ethane, 1,1,2-tris (4 '-(1'-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4'-(1'-ethoxypropyloxy) phenyl) Ethane etc. are mentioned.
    [104] As the basic compound of the component (E), a compound capable of suppressing the diffusion rate when the acid generated in the photoacid generator diffuses in the resist film is suitable, and the diffusion of the acid in the resist film by the combination of such a basic compound is preferable. The speed is suppressed, the resolution is improved, the sensitivity change after exposure can be suppressed, the substrate and the environment dependence can be reduced, and the exposure margin, the pattern profile, and the like can be improved.
    [105] Examples of the basic compound of the component (E) include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group and nitrogen-containing compounds having sulfonyl groups, The nitrogen compound which has a hydroxy group, the nitrogen compound which has a hydroxyphenyl group, an alcoholic nitrogen compound, an amide derivative, an imide derivative, etc. are mentioned.
    [106] Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified, As secondary aliphatic amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, and dish Clopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethyl Ethylenediamine, N, N-dimethyltetraethylenepentamine and the like are exemplified, As aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, Trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N , N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like.
    [107] In addition, examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethyl aniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-di Nitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole , 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, and the like), oxazole derivatives (for example, oxazole, isoxazole, etc.), thiazole Derivatives (e.g. thiazole, isothiazole, etc.), imidazole derivatives (e.g. imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.) , Pyrazole derivatives, plazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine , Pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1) -Butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, Dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives , Pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine induction Sieve, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indolin derivatives, quinoline derivatives (e.g. quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnaline derivatives, quinazoline Derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.
    [108] In addition, examples of the nitrogen-containing compound having a carboxyl group include amino benzoic acid, indole carboxylic acid, and amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylosin, leucine, Methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine and the like), and the like, and pyridine sulfonic acid, p-toluenesulfonic acid pyridinium, etc. Illustrative examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, and monoethanol. Amine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodie Ol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2 -Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxy Hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinucridinol , 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Is illustrated. Examples of the amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Phthalimide, succinimide, maleimide, etc. are illustrated as an imide derivative.
    [109] Moreover, 1 type, or 2 or more types chosen from the basic compound represented by following formula (7) can also be added.
    [110] N (X) n (Y) 3-n
    [111] In the formula, n = 1, 2 or 3. The side chain X may be the same or different and may be represented by the following Formulas 8a to 8c. Side chain Y represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may be the same or different, and may contain an ether group or a hydroxyl group.
    [112]
    [113]
    [114]
    [115] Here, R 300 , R 302 and R 305 are linear or branched alkyl groups having 1 to 4 carbon atoms, and R 301 and R 304 are hydrogen atoms or linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. And may contain one or more hydroxy groups, ether groups, ester groups, and lactone rings.
    [116] R 303 is a single bond, straight or branched alkyl group having 1 to 4 carbon atoms, R 306 is a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a hydroxy group, ether group, ester group, or lactone ring It may contain one or more.
    [117] The following are specifically mentioned as a compound represented by the said General formula (7).
    [118] Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {-2 -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- { 2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacoic acid, 4,7 , 13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eichoic acid, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12- Crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2- Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2- valeryloxyethyl) amine Tris (2-pivaloyloxyethyl) Min, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl ) Amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis ( 2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxy Ethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N -Bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine , N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl ) Methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- ( 2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2 -(Tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N -Bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxy Butoxy Carbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (Methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycar Carbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl ) Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) Ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-ace Methoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-meth Tilbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine , Tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (Diethylamino) -δ-valerolactone can be exemplified, but is not limited to these.
    [119] In addition, a basic compound can be used individually by 1 type or in combination of 2 or more types, It is preferable that the compounding quantity mixed 0-2 weight part, especially 0.01-1 weight part with respect to 100 weight part of solid content in a resist material. . When a compounding quantity exceeds 2 weight part, a sensitivity may fall too much.
    [120] In the chemically amplified positive resist material of the present invention, a surfactant for further improving applicability may also be added.
    [121] Examples of the surfactant include, but are not particularly limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene octyl Polyoxyethylene alkylallyl ethers such as phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, etc. Non-fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Polyoxyethylene sorbitan fatty acid ester Nonionic surfactant, F-top EF301, EF303, EF352 (Tochem product), Megapack F171, F172, F173 (Dainitken Ink Chemical Industry), Flode FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, West Fluorine-based surfactants such as Pron S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Sufinol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass) , Organosiloxane polymers KP341, X-70-092, X-70-093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid-based polyflop Nos. 75, No. 95 (Kyoeisha Oil and Chemicals Co., Ltd.) Among them, FC430, Ceflon S-381, Sufinol E1004, KH-20, and KH-30 are preferable. These can be used individually or in combination of 2 or more types.
    [122] The addition amount of surfactant in the chemically amplified positive resist material of this invention is 2 weight part or less with respect to 100 weight part of base resin in a resist material composition, Preferably it is 1 weight part or less.
    [123] A chemically amplified positive resist material containing (A) an organic solvent of the present invention, (B) a polymer compound having a repeating unit represented by the formula (1) or (2), and (C) an acid generator Although it does not specifically limit when using for various integrated circuit manufacture, A well-known lithography technique can be used.
    [124] Appropriate coating method such as spin coat, roll coat, flow coat, dip coat, spray coat, doctor coat, etc. on the substrate for integrated circuit manufacturing (Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coating, etc.) It apply | coats so that a coating film thickness may be set to 0.1-2.0 micrometers, and prebaking is carried out on a hotplate for 60 to 150 degreeC for 1 to 10 minutes, Preferably it is 80 to 120 degreeC for 1 to 5 minutes. Then, the target pattern is exposed through a predetermined mask at a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, gamma rays, synchrotron radiation and the like, preferably at an exposure wavelength of 300 nm or less. The exposure amount is preferably exposed to about 1 to 200 mJ / cm 2 , preferably about 10 to 100 mJ / cm 2 . Post exposure bake (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.
    [125] In addition, 0.1 to 5%, preferably 2 to 3% immersion (dip) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes using a developing solution of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) The target pattern is formed on a substrate by developing according to a conventional method such as a method, a puddle method, a spray method, or the like. In addition, the resist material of the present invention is particularly suitable for fine patterning by 254 to 193 nm of far ultraviolet rays, 157 nm of vacuum ultraviolet rays, electron beams, soft X-rays, X-rays, excimer lasers, γ-rays, and synchrotron radiation. . Moreover, when the said range deviates from an upper limit and a lower limit, the target pattern may not be obtained.
    [126] Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are described and this invention is demonstrated concretely, this invention is not limited to a following example.
    [127] Synthesis Example 1
    [128] Into a 2 L flask, 66.5 g of p-acetoxy styrene, 33.5 g of p-tert-amyloxystyrene, and 200 g of toluene were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 3.9g of AIBN was added as a polymerization initiator, and it heated for 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 DEG C to obtain 92 g of a white polymer. This polymer was dissolved in 0.27 L of methanol and 0.27 L of tetrahydrofuran again, 77 g of triethylamine and 15 g of water were added to carry out deprotection reaction and neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 61 g of a white polymer.
    [129] The obtained polymer was measured by 13 C, 1 H-NMR and GPC, and the following analysis results were obtained.
    [130] Copolymerization Ratio
    [131] Hydroxystyrene: p-tert-amyloxystyrene = 72.5: 27.5
    [132] Weight average molecular weight (Mw) = 16,100
    [133] Molecular weight distribution (Mw / Mn) = 1.73
    [134] This is called (poly-A).
    [135] Synthesis Example 2
    [136] To the 2 L flask, 200 g of toluene was added as 71.5 g of p-acetoxy styrene, 22.4 g of p-tert-amyloxystyrene, 8.1 g of methacrylic acid 1-ethylcyclopentyl ester, and a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 3.9g of AIBN was added as a polymerization initiator, and it heated for 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 DEG C to obtain 89 g of a white polymer. This polymer was dissolved in 0.27 L of methanol and 0.27 L of tetrahydrofuran again, 77 g of triethylamine and 14 g of water were added to carry out deprotection reaction and neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 55 g of a white polymer.
    [137] The obtained polymer was measured by 13 C, 1 H-NMR, and GPC, and the following analysis results were obtained.
    [138] Copolymerization Ratio
    [139] Hydroxystyrene: p-tert-amyloxystyrene: Methacrylic acid 1-ethylcyclopentyl ester = 70.9: 21.9: 7.2
    [140] Weight average molecular weight (Mw) = 17,000
    [141] Molecular weight distribution (Mw / Mn) = 1.70
    [142] This is called (poly-B).
    [143] Synthesis Example 3
    [144] Into a 2 L flask, 71.6 g of p-acetoxy styrene, 22.4 g of p-tert-amyloxystyrene, 6.1 g of methacrylic acid 1-ethyl norbornyl ester, and 200 g of toluene were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 3.9g of AIBN was added as a polymerization initiator, and it heated for 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C to obtain 85 g of a white polymer. The polymer was dissolved in 0.27 L of methanol and 0.27 L of tetrahydrofuran again, 77 g of triethylamine and 14 g of water were added to carry out dehydration protection reaction and neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 52 g of a white polymer.
    [145] The obtained polymer was measured by 13 C, 1 H-NMR, and GPC, and the following analysis results were obtained.
    [146] Copolymerization Ratio
    [147] Hydroxystyrene: p-tert-amyloxystyrene: Methacrylic acid 1-ethyl norbornyl ester = 73.8: 21.9: 4.3
    [148] Weight average molecular weight (Mw) = 17,500
    [149] Molecular weight distribution (Mw / Mn) = 1.66
    [150] This is called (poly-C).
    [151] Synthesis Example 4
    [152] Into a 2 L flask, 71.1 g of p-acetoxy styrene, 16.7 g of p-tert-amyloxystyrene, 12.2 g of methacrylic acid 1-ethyl norbornyl ester, and 200 g of toluene were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 3.8g of AIBN was added as a polymerization initiator, and it heated for 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C to obtain 83 g of a white polymer. The polymer was dissolved in 0.27 L of methanol and 0.27 L of tetrahydrofuran again, 77 g of triethylamine and 14 g of water were added to carry out deprotection reaction and neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 50 g of a white polymer.
    [153] The obtained polymer was measured by 13 C, 1 H-NMR and GPC, and the following analysis results were obtained.
    [154] Copolymerization Ratio
    [155] Hydroxystyrene: p-tert-amyloxystyrene: Methacrylic acid 1-ethyl norbornyl ester = 75.9: 16.1: 7.9
    [156] Weight average molecular weight (Mw) = 17,700
    [157] Molecular weight distribution (Mw / Mn) = 1.70
    [158] This is called (poly-D).
    [159] Synthesis Example 5
    [160] To the 2 L flask, 69.1 g of p-acetoxy styrene, 22.0 g of p-tert-amyloxystyrene, 8.3 g of methacrylic acid 1-ethyladamantyl ester, and 200 g of toluene were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 3.8g of AIBN was added as a polymerization initiator, and it heated for 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C to obtain 87 g of a white polymer. The polymer was dissolved in 0.27 L of methanol and 0.27 L of tetrahydrofuran again, 77 g of triethylamine and 14 g of water were added to carry out deprotection reaction and neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 53 g of a white polymer.
    [161] The obtained polymer was measured by 13 C, 1 H-NMR, and GPC, and the following analysis results were obtained.
    [162] Copolymerization Ratio
    [163] Hydroxystyrene: p-tert-amyloxystyrene: Methacrylic acid 1-ethyladamantyl ester = 73.1: 23.1: 3.8
    [164] Weight average molecular weight (Mw) = 16,300
    [165] Molecular weight distribution (Mw / Mn) = 1.78
    [166] This is called (poly-E).
    [167] Synthesis Example 6
    [168] To a 2 L flask, 68.3 g of p-acetoxy styrene, 20.4 g of p-tert-amyloxystyrene, 5.3 g of p-ethoxyethoxystyrene, and 200 g of toluene were added as a solvent. The reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After heating up to room temperature, 4.0g of AIBN was added as a polymerization initiator, and it heated up to 60 degreeC, and made it react for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 DEG C to obtain 89 g of a white polymer. The polymer was dissolved in 0.27 L of methanol and 0.27 L of tetrahydrofuran again, 77 g of triethylamine and 14 g of water were added to carry out deprotection reaction and neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 57 g of a white polymer.
    [169] The obtained polymer was measured by 13 C, 1 H-NMR, and GPC, and the following analysis results were obtained.
    [170] Copolymerization Ratio
    [171] Hydroxystyrene: p-tert-amyloxystyrene: ethoxyethoxystyrene = 74.0: 22.0: 4.0
    [172] Weight average molecular weight (Mw): 16,200
    [173] Molecular weight distribution (Mw / Mn) = 1.78
    [174] This is called (poly-F).
    [175] Comparative Synthesis Example
    [176] The following two component and three component polymers were synthesize | combined by the method similar to the said synthesis example, and it was set as the polymer for comparative examples. The analysis result is shown.
    [177] Hydroxystyrene: tert-butoxystyrene = 71: 29
    [178] Weight average molecular weight (Mw) = 16,100
    [179] Molecular weight distribution (Mw / Mn) = 1.70
    [180] This is called (poly-G).
    [181] Hydroxystyrene: tert-butoxystyrene: Methacrylic acid 1-ethyl norbornyl ester = 75.9: 18.8: 5.3
    [182] Weight average molecular weight (Mw) = 16,700
    [183] Molecular weight distribution (Mw / Mn) = 1.75
    [184] This is called (poly-H).
    [185] Moreover, the resist liquid was combined with the composition shown in Table 1, 2. In that case, poly-A to H shown in the said synthesis example and the comparative synthesis example were used for the high molecular compound of the resist material shown in Table 1, 2, and the other composition component used the thing shown below.
    [186] PAG1: 10-campasulfonic acid (4-butoxyphenyl) diphenylsulfonium
    [187] PAG2: 4- (4'-methylphenylsulfonyloxy) phenylsulfonic acid (4-tert-butylphenyl) diphenylsulfonium
    [188] Dissolution Inhibitor A: Bis (4- (2'-tetrahydropyranyloxy) phenyl) methane
    [189] Basic Compound A: Tris (2-methoxyethyl) amine
    [190] Surfactant A: FC-430 (made by Sumitomo 3M company)
    [191] Surfactant B: Supron S-381 (made by Asahi Glass Co., Ltd.)
    [192] Solvent A: Propylene Glycol Methyl Ether Acetate
    [193] Solvent B: ethyl lactate
    [194] Composition (part by weight)Example 1Example 2Example 3Example 4 poly-Apoly-Bpoly-Cpoly-D80 ----80----80---- 80 PAG1PAG221212121 Soluble Blocking Agents A Basic Compound B-0.2-0.2-0.2-0.2 Surfactant A Surfactant B0.070.070.070.070.070.070.070.07 Solvent A Solvent B300130300130300130300130
    [195] Composition (part by weight)Example 5Example 6Comparative Example 1Comparative Example 2 poly-Epoly-Fpoly-Gpoly-H80 ----80----80---- 80 PAG1PAG221212111 Soluble Blocking Agents A Basic Compound B-0.2-0.2-0.2-0.2 Surfactant A Surfactant B0.070.070.070.070.070.070.070.07 Solvent A Solvent B300130300130300130300130
    [196] After filtering the obtained resist solution with a 0.2 micrometer Teflon filter, this resist liquid was spin-coated on a silicon wafer, and it applied at 0.4 micrometer.
    [197] Then, the silicon wafer was baked for 90 seconds on a hot plate at 100 ° C. Exposure was performed using an excimer laser stepper (NSR2005EXNA = 0.6, Nikon Corp.), and a post exposure bake (PEB) was performed at 110 ° C. for 90 seconds, and development was carried out in an aqueous solution of 2.38% of tetramethylammonium hydroxide. When it was performed, positive patterns (Examples 1 to 6 and Comparative Examples 1 and 2) were obtained.
    [198] The obtained resist pattern was evaluated as follows.
    [199] Resist pattern evaluation method:
    [200] The exposure amount which resolves the top and bottom of a 0.15 micrometer line and space by 1: 1 was made into the optimal exposure amount (sensitivity: Eop), and the minimum line width of the separated line and space in this exposure amount was made into the resolution of an evaluation resist. . Moreover, the cross section of the resist was observed for the shape of the resolved resist pattern using the scanning electron microscope.
    [201] In addition, the PED stability of the resist was evaluated by the variation of the line width after PEB (post exposure bake) after standing for 24 hours after exposure at the optimum exposure dose. The smaller this variation, the richer the PED stability.
    [202] Table 3 shows the evaluation results of the resist pattern.
    [203] Sensitivity (mJ / cm 2 )Resolution (μm)Profile shapeDimensional Stability of PED After 24 Hours (nm) Example 1 Example 2 Example 3 Example 4 Example 5 Example 62829292729280.130.120.120.130.120.13Rectangle rectangle rectangle center concave shape rectangle rectangle-8-6-5-5-7-12 Comparative Example 1 Comparative Example 235320.150.15Taper Shape Tapered Feel-8-14
    [204] According to the present invention, the alkali dissolution rate contrast before and after exposure is significantly high by blending tert-amyloxystyrene by the action of an acid and using a high molecular compound used as a reactive group to increase solubility in alkali to the resist material as a base resin. When using tert-butoxy styrene with high sensitivity, a resist such as a chemically amplified resist material which realizes high resolution in a bake temperature range of 100 to 110 ° C which is difficult and is particularly preferable as a fine pattern forming material for ultra-LSI manufacturing It is possible to provide the material.
    权利要求:
    Claims (6)
    [1" claim-type="Currently amended] A resist material comprising a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following formula (1).
    <Formula 1>

    In formula, R <1> represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R <2> represents a hydrogen atom, a hydroxyl group, a halogen atom, or a trifluoromethyl group, n Is 0 or a positive integer of 1 to 4;
    [2" claim-type="Currently amended] A resist material comprising a polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following formula (2).
    <Formula 2>

    In formula, R <1> , R <3> represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, a halogen atom, or a trifluoromethyl group, R <2> represents a hydrogen atom, a hydroxy group, a halogen atom, or a trifluoromethyl group R 4 represents a hydrogen atom, a halogen atom, a trifluoromethylhydroxymethyl group, or -OR, and R represents a linear, branched or cyclic alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group or Represents a trialkylsilyl group, R 5 represents a hydrogen atom or a methyl group, R 6 represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, a halogen atom or a trifluoromethyl group, and R 7 represents a straight chain having 4 to 30 carbon atoms. Chain, branched or cyclic alkyl group, n is 0 or a positive integer of 1 to 4, m is 0 or a positive integer of 1 to 5, p, r, s is 0 or positive , Q is a positive number.)
    [3" claim-type="Currently amended] (A) an organic solvent,
    (B) the polymer compound according to claim 1 or 2 as a base resin,
    (C) acid generator
    A chemically amplified positive resist material comprising a.
    [4" claim-type="Currently amended] (A) an organic solvent,
    (B) the polymer compound according to claim 1 or 2 as a base resin,
    (C) an acid generator,
    (D) Dissolution stopper
    A chemically amplified positive resist material comprising a.
    [5" claim-type="Currently amended] The chemically amplified positive resist material according to claim 3 or 4, further comprising a basic compound as an additive (E).
    [6" claim-type="Currently amended] The process of apply | coating the resist material of any one of Claims 3-5 on a board | substrate, and then heat-processing, exposing with high energy rays or an electron beam through a photomask, and heat-processing as needed. And developing using a developing solution.
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    同族专利:
    公开号 | 公开日
    JP3821217B2|2006-09-13|
    TW200300038A|2003-05-01|
    US6949323B2|2005-09-27|
    US20030118934A1|2003-06-26|
    JP2003131384A|2003-05-09|
    EP1308782B1|2012-09-05|
    TWI249649B|2006-02-21|
    KR100676801B1|2007-02-01|
    EP1308782A1|2003-05-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-10-30|Priority to JPJP-P-2001-00331757
    2001-10-30|Priority to JP2001331757A
    2002-10-29|Application filed by 신에쓰 가가꾸 고교 가부시끼가이샤
    2003-06-27|Publication of KR20030052966A
    2007-02-01|Application granted
    2007-02-01|Publication of KR100676801B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2001-00331757|2001-10-30|
    JP2001331757A|JP3821217B2|2001-10-30|2001-10-30|Resist material and pattern forming method|
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